Spectrophotometric pH-measurement in the ocean: requirements, design and testing of an autonomous charge-coupled device detector system

Karsten Friis, Arne Koertzinger, Douglas DWR Wallace

Limnol. Oceanogr. Methods 2:126-136 (2004) | DOI: 10.4319/lom.2004.2.126

ABSTRACT: A newly designed system for high quality discrete spectrophotometric measurements of pHT using a low-cost CCD detector is described. Considerations and requirements for the choice of spectrophotometers with a CCD detector instead of scanning spectrophotometers with photomultiplier detector are elucidated. The presented system is evaluated in the laboratory for system accuracy and short-term precision and at-sea for long-term precision and at-sea capability. Derived system characteristics are a (1s) short-term precision of ± 0.0012 pH units and a (1s) long-term precision at-sea of ± 0.0032 pH units based on Certified Reference Materials (CRM). Such long-term precision is equivalent to a deviation of ± 1.1 to 2.2 µmol kg-1 in total dissolved inorganic carbon (TCO2) and ± 1.4 to 2.1 µmol kg-1 in total alkalinity (TA), depending on temperature and the TCO2/TA ratio. Over-determination of the CO2 system (TCO2, TA, pHT) from surface-to-deep water profiles support the accuracy and precision assessment in comparison to earlier data. With careful design and testing low-cost CCD spectrophotometers can be used for high accuracy pH-measurements.